CN106398116B - A kind of preparation method of P10 glue solution for copper-clad plate - Google Patents
A kind of preparation method of P10 glue solution for copper-clad plate Download PDFInfo
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- CN106398116B CN106398116B CN201610752393.0A CN201610752393A CN106398116B CN 106398116 B CN106398116 B CN 106398116B CN 201610752393 A CN201610752393 A CN 201610752393A CN 106398116 B CN106398116 B CN 106398116B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/752—Corrosion inhibitor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a kind of preparation methods of P10 glue solution for copper-clad plate comprising following step: (1) under agitation, mixture A being mixed with liquid-state epoxy resin；Then shearing 3-5 hours is carried out with the speed of 2500-3000rpm, then is mixed with mixture B, obtain mixture C；Mixture A is mixed to get by the solvent of solid epoxy resin and 40%-60%；Mixture B is mixed to get by phenolic resin and remaining solvent；(2) under agitation, mixture C, curing accelerator and fluorescent whitening agent are mixed, then mix, sheared with the speed of 2000-3000rpm, after curing with inorganic filler again to obtain the final product.Glue obtained by preparation method of the present invention not only has good adhesive force and anti-ultraviolet function, also has good heat resistance, has excellent resistance to acid and alkali, solvent resistance, heat resistance.
Description
Technical field
The present invention relates to a kind of preparation methods of P10 glue solution for copper-clad plate.
Background technique
In recent years, a kind of resistance to ultra violet discoloration and the copper-clad plate (P10 that resistance to thermochromism is excellent, LED lamplight radiant output is high
Copper-clad plate), rapidly developed in LED (light emitting diode) application field.It has become meets particularity in copper-clad plate
A kind of product that can be required.
However, temperature raising can be such that transparent epoxy resin degree is decreased obviously, Barton research discovery temperature reaches 140 DEG C
When, epoxy resin is seriously degenerated, and LED light service life is influenced, and when temperature reaches 150 DEG C, transparent epoxy resin degree is decreased obviously,
So as to cause LED lamplight radiant output decrease.
Presently, it generallys use plus appropriate inorganic filler reduces copper-clad plate thermal expansion coefficient.Copper foil, glass-fiber-fabric, resin
Three's thermal expansion coefficient difference is larger, and appropriate filler, which is added, can be relieved the difference of expanding with heat and contract with cold of three, in this way can be to avoid high temperature
Lower three deforms different caused route deformation fracture, to avoid causing catastrophic to fail.But P10 copper-clad plate is come
It says, its production cost is still higher at present, and the resin transparent degree decline under high temperature still has, service life and resistance to ultraviolet
It can linearly need to be further increased.
Summary of the invention
Technical problem solved by the invention is to overcome existing the at high cost of P10 copper-clad plate, resistance to acid and alkali and resistance to
Hot and epoxy resin influences the defects of LED lamplight radiant output weakens because temperature resistant transparent degree reduces, and provides a kind of P10 and covers
Copper sheet glue, prepreg and copper-clad plate and preparation method.Glue of the invention not only has good adhesive force and anti-purple
Outside line function also has good heat resistance, has excellent resistance to acid and alkali, solvent resistance, heat resistance.By glue of the invention
Further prepreg obtained and copper-clad plate have the physicochemical property as it, and more existing product is whiter and smooth
Light can make LED light seem whiter, brighter and more bright-coloured.
The present invention solves above-mentioned technical problem by the following technical programs.
The present invention provides a kind of P10 glue solution for copper-clad plate, are made by following raw materials, and the raw material includes following weight
The component of part: 300-400 parts of liquid-state epoxy resins, 100-200 parts of solid epoxy resins, 175-235 parts of phenolic resin, 0.3-
0.4 part of curing accelerator, 280-360 parts of solvents, 100-600 parts of inorganic fillers and 0.5-1.0 parts of fluorescent whitening agents.
Wherein, the liquid-state epoxy resin and the solid epoxy resin can be used various normal in this field copper-clad plate glue
Advise the epoxy resin used；The liquid-state epoxy resin is preferably bisphenol type liquid-state epoxy resin, is more preferably bisphenol A-type liquid
State epoxy resin.The solid epoxy resin is preferably bisphenol type solid epoxy resin, is more preferably bisphenol A-type solid epoxidic
Resin.In the present invention, using the different epoxy resin of polymerization degree n (molecular weight or epoxide equivalent).In general, epoxide equivalent is got over
High (molecular weight is bigger) flexibility is better, to improve the flexibility of plate；Increase curing reaction degree simultaneously, shortens reaction
Time.It in the present invention, while being arranged in pairs or groups using solid and liquid-state epoxy resin, the heat expansion of subsequent prepreg obtained can be made
Contraction coefficients are minimum, have anti-ultraviolet function.The epoxide equivalent of the liquid-state epoxy resin is preferably 195-200g/eq
(i.e. gram/equivalent)；The epoxide equivalent of the solid epoxy resin is preferably 980-1070g/eq.
The parts by weight of the liquid-state epoxy resin are preferably 320-380 parts；The parts by weight of the solid epoxy resin
Preferably 120-180 parts of number.
In the present invention, phenolic resin is used to replace current conventional use of dicyandiamide, uses as curing agent.Invention human hair
It is existing, using phenolic resin come subotituted dicyardiamide, toughness can not only be enhanced, cohesion is strong, excellent storage stability, moulded manufacturability
It is good, it can also act as resin content, to reduce the input amount of epoxy resin.
The softening point of the phenolic resin is preferably 80-120 DEG C, is more preferably 85-100 DEG C, such as 95-100 DEG C.This
In invention, the softening point refers to the temperature of substance softening, refers generally to temperature when amorphous polymer starts softening, i.e., of the invention
Described in phenolic resin start soften when temperature.
The parts by weight of the phenolic resin are preferably 190-210 parts.
Wherein, the curing accelerator can be curing accelerator commonly used in the art, and preferably imidazoles solidify
Promotor is more preferably 2-methylimidazole and/or 2- phenylimidazole.The parts by weight of the curing accelerator are preferably
0.35-0.40 parts.When the curing accelerator is 2-methylimidazole and 2- phenylimidazole, the 2-methylimidazole and 2- phenyl miaow
The weight ratio of azoles is preferably (1-2): (4-5).
Wherein, the solvent can be solvent commonly used in the art, preferably ketones solvent and/or ether solvent,
It is more preferably one of acetone, butanone and propylene glycol monomethyl ether or a variety of.The parts by weight of the solvent are preferably 360-370
Part.When the solvent is acetone, butanone and propylene glycol monomethyl ether, the weight ratio of the acetone, butanone and propylene glycol monomethyl ether is preferable
Ground is (2-4): (1-3): (1-2).
Wherein, the inorganic filler can be inorganic filler commonly used in the art, preferably aluminium hydroxide, hydroxide
One of magnesium, calcium oxide, silica and talcum powder are a variety of.The parts by weight of the inorganic filler are preferably 100-
300 parts.When the inorganic filler is aluminium hydroxide, silica and talcum powder, the aluminium hydroxide, silica and talcum
The weight ratio of powder is preferably (3-5): (6-8): (1-2).
Wherein, the fluorescent whitening agent can be the fluorescent whitening agent for being usually used in the fabric brightenings such as cotton and nylon, preferably
The Sunwhite line fluorescent brightening agent of (granary) Fine Chemical Co., Ltd, rising sun Thailand production, as Sunwhite FG-E fluorescence increases
White dose.In the present invention, fluorescent whitening agent is used, sightless ultraviolet light not only can be absorbed, and (wave-length coverage is about 60-
380nm), it is converted into the visible light of longer wavelengths of blue light or purple, and then compensates undesired micro- Huang in plate matrix
Color, while reflecting than original incident more visible lights (wavelength is in 400-600nm), so as to be used in subsequent copper-clad plate
In so that LED light is seemed whiter, brighter, more bright-coloured.
The present invention also provides a kind of preparation methods of P10 glue solution for copper-clad plate comprising following step:
(1) under agitation, mixture A is mixed with the liquid-state epoxy resin；Then with 2500-3000rpm's
Speed carries out shearing 3-5 hours, then is mixed with mixture B, and mixture C is obtained；
The mixture A is mixed to get by the solvent of the solid epoxy resin and 40%-60%；The mixture
B is mixed to get by the phenolic resin and the remaining solvent；
(2) under agitation, the mixture C, the curing accelerator and the fluorescent whitening agent are mixed, then
It mixes, is sheared with the speed of 2000-3000rpm, after curing with the inorganic filler again to obtain the final product.
It is used after in advance being mixed all solvents, institute by common sense in the field when solvent uses multi-solvents type
It states to mix to be subject to and be uniformly mixed, stirred 0.1-0.2 hours preferably under the revolving speed of 500-800rpm.
It is described to mix subject to so that the solid epoxy resin is completely dissolved in the preparation of the mixture A, preferably
For with the revolving speed of 1500-2000rpm stirring 6-8 hours.
It is described to mix subject to so that the phenolic resin is completely dissolved in the preparation of the mixture B, preferably with
The revolving speed of 1500-2000rpm stirs 6-8 hours.
In step (1), the method and condition of the stirring can be the method and condition of this field routine.The stirring turns
Speed is preferably 1500-2000rpm.The time of the stirring is preferably 3-5 hours.
In step (1), the mixed method and condition in " being mixed with mixture B " can be the method for this field routine
And condition, preferably stirred 3-5 hours with the revolving speed of 1500-2000rpm.
In step (2), the time of the shearing is preferably 0.5-1.5 hours.The speed of the shearing is preferably
2000-2500rpm。
In step (2), the method and condition of the curing can be the method and condition of this field routine.The curing compared with
Goodly for the revolving speed of 1000-1500rpm stirring 6-10 hours.
The present invention also provides a kind of preparation methods of P10 copper-clad plate prepreg comprising following step: in electronics
The P10 glue solution for copper-clad plate is coated on grade fiberglass cloth, after drying to get.
The E-glass cloth is the E-glass cloth in this field in conventional use of prepreg raw material.
Preferably, the E-glass cloth is electronic-grade glass fiber cloth 7628.
Preferably, the equipment of the coating is gluing machine.
Preferably, the speed of the coating is 17-25m/min；It is more preferably 16-19m/min, such as 18m/min.
Preferably, the temperature of the drying is 170-230 DEG C；It is more preferably 200-220 DEG C.
The present invention also provides one kind P10 copper-clad plate prepreg as made from above-mentioned preparation method.
In the present invention, the resin content (RC) of the P10 copper-clad plate prepreg is generally 40-60%.The P10 covers
The gel time (GT) of copper sheet prepreg is generally 65-85s.P10 copper-clad plate prepreg fluidity (RF) one
As be 18-25%.The fugitive constituent of the P10 copper-clad plate prepreg is generally below 0.25%.4 inch of * 4 inch area
The weight (PPW) of the P10 copper-clad plate prepreg is generally in 4.0-4.6g.
The present invention also provides a kind of preparation methods of P10 copper-clad plate comprising following steps:
1. lamination: several described prepregs fold and are matched, lamination is formed；Two lateral surfaces of lamination one side or
It is covered with copper foil on two sides, obtains semi-finished product；
2. by the semi-finished product carry out hot pressing compacting to get.
In the present invention, the folded method for stacking prepreg with for copper-clad plate preparation process field routine, usually
It is neatly stacked with several identical prepregs of size and shape, i.e. what each side of prepreg was all aligned stacks.This
In invention, described folded with pressure is not needed, described fold follows four big principles: gel content high level matches with low level principle, cloth type one with general
Cause principle, symmetrical configuration principle and left and right collocating principle.
Step 1. in, the copper foil can be copper foil commonly used in the art.
Step 2. in, the method and condition of hot pressing compacting can be the method and condition of this field routine.The hot pressing
The pressure of compacting is preferably 20-40kg/cm2；The temperature of the hot pressing compacting is preferably 90-220 DEG C；The hot pressing compacting
Time be preferably 80-120min.
In the present invention, the preparation method of the copper-clad plate carries out subsequent sharp processing and inspection process, also generally with true
Protect the quality of product.
The P10 copper-clad plate as obtained by the preparation method that the present invention also provides a kind of.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
P10 glue solution for copper-clad plate of the invention not only has good adhesive force and anti-ultraviolet function, also has fine
Heat resistance, have excellent resistance to acid and alkali, solvent resistance, heat resistance.By the further semi-solid preparation obtained of glue of the invention
Piece and copper-clad plate have a physicochemical property as it, and more existing product is whiter and smooth, and LED light can be made aobvious
It is get Geng Bai, brighter and more bright-coloured.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiments, number used is parts by weight.
In following embodiments, fluorescent whitening agent used is safe (granary) the Fine Chemical Co., Ltd production of the rising sun
Sunwhite FG-E system fluorescent whitening agent.
In following embodiments, the epoxide equivalent of used bisphenol A-type liquid epoxy resin is 195-200g/eq；Made
The epoxide equivalent of bisphenol A-type solid epoxy resin is 980-1070g/eq.
Embodiment 1
The composition of raw materials of P10 glue solution for copper-clad plate is as follows:
(softening point is for 370 parts of bisphenol A-type liquid epoxy resin, 160 parts of bisphenol A-type liquid epoxy resin, phenolic resin
95-100 DEG C) 200 parts, 0.20 part of 2- phenylimidazole, 0.15 part of 2-methylimidazole, 140 parts of acetone, 100 parts of butanone, propylene glycol first
130 parts of ether, 300 parts of aluminium hydroxide, 100 parts of soft silicon, 50 parts of talcum powder and 0.5 part of fluorescent whitening agent.
Glue the preparation method is as follows:
(1) acetone, butanone and propylene glycol monomethyl ether are stirred 0.1 hour under the revolving speed of 500rpm and obtains mixed solvent；It takes
Half mixed solvent is mixed with solid epoxy resin, is stirred 6 hours with 1500 revolving speed, is obtained mixture A；Take another meromict
Solvent is mixed with phenolic resin, is stirred 6 hours with the revolving speed of 1500rpm, is obtained mixture B；
Under the speed of agitator of 1500rpm, mixture A is mixed with liquid-state epoxy resin, stir 6-8 hours, then with
The speed of 2500rpm carries out shearing 6 hours；It is mixed then at mixture B, is stirred 3 hours, obtained with the revolving speed of 1500rpm
Mixture C；
(2) under agitation, mixture C, 2- phenylimidazole, 2-methylimidazole and fluorescent whitening agent are mixed, then
It is mixed with aluminium hydroxide, soft silicon and talcum powder, shearing 0.5 hour is carried out with the speed of 2000rpm, in turning with 1000rpm
Speed stirring cured within 6 hours to get.
The preparation method of P10 copper-clad plate prepreg: institute is coated on electronic-grade glass fiber cloth 7628 with gluing machine
State P10 glue solution for copper-clad plate, after drying to get.The control parameter of P10 copper-clad plate prepreg is as follows:
Oven for gluing machine temperature: 210 DEG C；
Glue speed: 19m/min；
Resin content: RC is up to 45%；
The gel time GT:70s of prepreg；
The fluidity RF:19% of prepreg；
The fugitive constituent VC:0.25% of prepreg；
The weight PPW:4.2g of prepreg.
P10 copper-clad plate (1.5mm plate) the preparation method is as follows:
1. lamination: 6 7628 prepregs fold and are matched, lamination is formed；It is covered in the one side of two lateral surfaces of lamination
The copper foil of upper 12 μ m-thick, obtains semi-finished product；
2. by semi-finished product carry out hot pressing compacting to get；Hot pressing pressure: 30kg/cm2；Hot pressing press temperature: 175 DEG C；Hot pressing
Pressing time: 80min.
Through detecting, the performance parameter of obtained P10 copper-clad plate is as shown in table 1.
Table 1
| Pilot project | Unit | Examination criteria | Embodiment 1 |
| 1. thermal decomposition temperature (Td) | ℃ | 10 DEG C/min, N, 5%WtLoss | 401 |
| 2. anti-flammability | - | UL94V-0 | V-0 |
| 3. thermal stress, 288 DEG C, 20 seconds | - | Surface without layering, without blistering | Without destruction |
| 4. heat resistance, 288 DEG C (TMA method) | Min | ≥30 | 60 |
| 5.Tg value, (DSC method) | ℃ | ≥170 | 180 |
| 6. water absorption rate, maximum value | % | ≤0.5 | 0.12 |
| 7. chemical resistance (process solvent infusion method) | - | 60 minutes colour-fast | Without destruction |
| 8. peel strength | LBS/IN | ≥5 | 8.1 |
Seen from table 1, P10 copper-clad plate comprehensive performance obtained by embodiment 1 is good.
In addition, carrying out ocular estimate with prepreg to obtained P10 copper-clad plate, it is commercially for relative to existing
The prepreg for preparing P10 copper-clad plate is whiter, and more smooth；Through detecting, aging examination is carried out at 140-150 DEG C
It tests, is reduced under the transparency of the P10 copper-clad plate prepreg, therefore obtained P10 copper-clad plate making in actual use
It is long with the service life, and not will cause LED lamplight radiant output decrease.
Embodiment 2
The composition of raw materials of P10 glue solution for copper-clad plate is as follows:
350 parts of bisphenol A-type liquid epoxy resin, 150 parts of bisphenol A-type solid-liquid epoxy resin, phenolic resin (softening point
It is 95-100 DEG C) 205 parts, 0.10 part of 2- phenylimidazole, 0.25 part of 2-methylimidazole, 130 parts of acetone, 110 parts of butanone, propylene glycol
130 parts of methyl ether, 350 parts of aluminium hydroxide, 50 parts of silica 1,60 parts of talcum powder and 0.6 part of fluorescent whitening agent.
Glue the preparation method is as follows:
(1) acetone, butanone and propylene glycol monomethyl ether are stirred 0.2 hour under the revolving speed of 800rpm and obtains mixed solvent；It takes
40% mixed solvent is mixed with solid epoxy resin, is stirred 8 hours with the revolving speed of 2000rpm, is obtained mixture A；It takes remaining mixed
Bonding solvent is mixed with phenolic resin, is stirred 8 hours with the revolving speed of 2000rpm, is obtained mixture B；
Under the speed of agitator of 2000rpm, mixture A is mixed with liquid-state epoxy resin, stir 8 hours, then with
The speed of 3000rpm carries out shearing 8 hours；It is mixed then at mixture B, is stirred 3-5 hours, obtained with the revolving speed of 2000rpm
To mixture C；
(2) under agitation, mixture C, 2- phenylimidazole, 2-methylimidazole and fluorescent whitening agent are mixed, then
It is mixed with aluminium hydroxide, silica and talcum powder, shearing 1.5 hours is carried out with the speed of 2500rpm, with 1500rpm's
Revolving speed stir cured within 10 hours to get.
The preparation method of P10 copper-clad plate prepreg: institute is coated on electronic-grade glass fiber cloth 7628 with gluing machine
State P10 glue solution for copper-clad plate, after drying to get.The control parameter of P10 copper-clad plate prepreg is as follows:
Oven for gluing machine temperature: 220 DEG C；
Glue speed: 21m/min；
Resin content: RC is up to 55%；
The gel time GT:75s of prepreg；
The fluidity RF:18% of prepreg；
The fugitive constituent VC:0.20% of prepreg；
The weight PPW:4.1g of prepreg.
P10 copper-clad plate (1.0mm plate) the preparation method is as follows:
1. lamination: 4 7628 prepregs fold and are matched, lamination is formed；It is covered on the two sides of two lateral surfaces of lamination
The copper foil of upper 15 μ m-thick, obtains semi-finished product；
2. by semi-finished product carry out hot pressing compacting to get；Hot pressing pressure: 32kg/cm2；Hot pressing press temperature: 185 DEG C；Hot pressing
Pressing time: 90min.
Through detecting, the performance parameter of obtained P10 copper-clad plate is as shown in table 2.
Table 2
| Pilot project | Unit | Examination criteria | Embodiment 1 |
| 1. thermal decomposition temperature (Td) | ℃ | 10 DEG C/min, N, 5%WtLoss | 385 |
| 2. anti-flammability | - | UL94V-0 | V-0 |
| 3. thermal stress, 288 DEG C, 20 seconds | - | Surface without layering, without blistering | Without destruction |
| 4. heat resistance, 288 DEG C (TMA method) | Min | ≥30 | 80 |
| 5.Tg value, (DSC method) | ℃ | ≥170 | 175 |
| 6. water absorption rate, maximum value | % | ≤0.5 | 0.19 |
| 7. chemical resistance (process solvent infusion method) | - | 60 minutes colour-fast | Without destruction |
| 8. peel strength | LBS/IN | ≥5 | 7.8 |
As can be seen from Table 2, P10 copper-clad plate comprehensive performance obtained by embodiment 2 is good.
In addition, carrying out ocular estimate with prepreg to obtained P10 copper-clad plate, it is commercially for relative to existing
The prepreg for preparing P10 copper-clad plate is whiter, and more smooth；Through detecting, aging examination is carried out at 140-150 DEG C
It tests, is reduced under the transparency of the P10 copper-clad plate prepreg, therefore obtained P10 copper-clad plate making in actual use
It is long with the service life, and not will cause LED lamplight radiant output decrease.
Embodiment 3
The composition of raw materials of P10 glue solution for copper-clad plate is as follows:
(softening point is for 300 parts of bisphenol A-type liquid epoxy resin, 200 parts of bisphenol A-type solid epoxy resin, phenolic resin
95-100 DEG C) 210 parts, 0.25 part of 2- phenylimidazole, 0.10 part of 2-methylimidazole, 140 parts of acetone, 120 parts of butanone, propylene glycol first
100 parts of ether, 400 parts of aluminium hydroxide, 130 parts of silicon powder, 70 parts of talcum powder and 0.4 part of fluorescent whitening agent.
Glue the preparation method is as follows:
(1) acetone, butanone and propylene glycol monomethyl ether are stirred 0.15 hour under the revolving speed of 600rpm and obtains mixed solvent；It takes
40% mixed solvent is mixed with solid epoxy resin, is stirred 7 hours with the revolving speed of 1800rpm, is obtained mixture A；It takes remaining mixed
Bonding solvent is mixed with phenolic resin, is stirred 7 hours with the revolving speed of 1800rpm, is obtained mixture B；
Under the speed of agitator of 1800rpm, mixture A is mixed with liquid-state epoxy resin, stir 6-8 hours, then with
The speed of 2700rpm carries out shearing 7 hours；It is mixed then at mixture B, is stirred 3-5 hours, obtained with the revolving speed of 1800rpm
To mixture C；
(2) under agitation, mixture C, 2- phenylimidazole, 2-methylimidazole and fluorescent whitening agent are mixed, then
It is mixed with aluminium hydroxide, silicon powder and talcum powder, shearing 1 hour is carried out with the speed of 2200rpm, with the revolving speed of 1200rpm
Stirring cured within 8 hours to get.
The preparation method of P10 copper-clad plate prepreg: institute is coated on electronic-grade glass fiber cloth 7628 with gluing machine
State P10 glue solution for copper-clad plate, after drying to get.The control parameter of P10 copper-clad plate prepreg is as follows:
Oven for gluing machine temperature: 215 DEG C；
Glue speed: 18m/min；
Resin content: RC is up to 60%；
The gel time GT:65s of prepreg；
The fluidity RF:19% of prepreg；
The fugitive constituent VC:0.22% of prepreg；
The weight PPW:4.4g of prepreg.
P10 copper-clad plate (0.8mm plate) the preparation method is as follows:
1. lamination: 3 7628 prepregs fold and are matched, lamination is formed；It is covered on the two sides of two lateral surfaces of lamination
The copper foil of upper 18 μ m-thick, obtains semi-finished product；
2. by semi-finished product carry out hot pressing compacting to get；Hot pressing pressure: 35kg/cm2；Hot pressing press temperature: 170 DEG C；Hot pressing
Pressing time: 95min.
Through detecting, the performance parameter of obtained P10 copper-clad plate is as shown in table 3.
Table 3
Seen from table 3, P10 copper-clad plate comprehensive performance obtained by embodiment 3 is good.
In addition, carrying out ocular estimate with prepreg to obtained P10 copper-clad plate, it is commercially for relative to existing
The prepreg for preparing P10 copper-clad plate is whiter, and more smooth；Through detecting, aging examination is carried out at 140-150 DEG C
It tests, is reduced under the transparency of the P10 copper-clad plate prepreg, therefore obtained P10 copper-clad plate making in actual use
It is long with the service life, and not will cause LED lamplight radiant output decrease.
Claims (10)
1. a kind of preparation method of P10 glue solution for copper-clad plate, which is characterized in that the raw material of the P10 glue solution for copper-clad plate includes
Following components in parts by weight: 300-400 parts of liquid-state epoxy resins, 100-200 parts of solid epoxy resins, 175-235 parts of phenolic aldehyde trees
Rouge, 0.3-0.4 part curing accelerator, 280-360 parts of solvents, 100-600 parts of inorganic fillers and 0.5-1.0 parts of fluorescent whitening agents；
The liquid-state epoxy resin is bisphenol A-type liquid epoxy resin, and the epoxide equivalent of the liquid-state epoxy resin is 195-
200g/eq；The solid epoxy resin is bisphenol A-type solid epoxy resin, and the epoxide equivalent of the solid epoxy resin is
980-1070g/eq；The softening point of the phenolic resin is 80-120 DEG C；
The preparation method includes the following steps:
(1) under agitation, mixture A is mixed with the liquid-state epoxy resin；Then with the speed of 2500-3000rpm
Shearing 3-5 hours is carried out, then is mixed with mixture B, mixture C is obtained；
The mixture A is mixed to get by the solvent of the solid epoxy resin and 40%-60%；The mixture B by
The phenolic resin and the remaining solvent are mixed to get；
(2) under agitation, by the mixture C, the curing accelerator and the fluorescent whitening agent mix, then again with
The inorganic filler mixing, is sheared, after curing with the speed of 2000-3000rpm to obtain the final product.
2. preparation method as described in claim 1, which is characterized in that the parts by weight of the liquid-state epoxy resin are 320-
380 parts；
And/or the parts by weight of the solid epoxy resin are 120-180 parts；
And/or the parts by weight of the phenolic resin are 190-210 parts；
And/or the curing accelerator is imidazoles curing accelerator；
And/or the parts by weight of the curing accelerator are 0.35-0.40 parts；
And/or the solvent is ketones solvent and/or ether solvent；
And/or the inorganic filler is one of aluminium hydroxide, magnesium hydroxide, calcium oxide, silica and talcum powder or more
Kind；
And/or the parts by weight of the inorganic filler are 100-300 parts；
And/or the fluorescent whitening agent is Sunwhite line fluorescent brightening agent.
3. preparation method as claimed in claim 2, which is characterized in that the softening point of the phenolic resin is 85-100 DEG C；
And/or the curing accelerator is 2-methylimidazole and/or 2- phenylimidazole；
And/or the solvent is one of acetone, butanone and propylene glycol monomethyl ether or a variety of；
And/or the inorganic filler is aluminium hydroxide, silica and talcum powder, the aluminium hydroxide, silica and talcum
The weight ratio of powder is (3-5): (6-8): (1-2)；
And/or the fluorescent whitening agent is Sunwhite FG-E fluorescent whitening agent.
4. preparation method as described in any one of claims 1-3, which is characterized in that the curing accelerator is 2-methylimidazole
With 2- phenylimidazole, the weight ratio of the 2-methylimidazole and 2- phenylimidazole is (1-2): (4-5)；
And/or the solvent is acetone, butanone and propylene glycol monomethyl ether, the weight ratio of the acetone, butanone and propylene glycol monomethyl ether is
(2-4): (1-3): (1-2).
5. preparation method as described in claim 1, which is characterized in that in the preparation of the mixture A, it is described be mixed into
The revolving speed of 1500-2000rpm stirs 6-8 hours.
6. preparation method as described in claim 1, which is characterized in that in the preparation of the mixture B, it is described be mixed into
The revolving speed of 1500-2000rpm stirs 6-8 hours.
7. preparation method as described in claim 1, which is characterized in that in step (1), the revolving speed of the stirring is 1500-
2000rpm；And/or in step (1), the time of the stirring is 3-5 hours.
8. preparation method as described in claim 1, which is characterized in that in step (1), in " being mixed with mixture B "
It is mixed into and is stirred 3-5 hours with the revolving speed of 1500-2000rpm.
9. preparation method as described in claim 1, which is characterized in that in step (2), the time of the shearing is 0.5-1.5
Hour；And/or in step (2), the speed of the shearing is 2000-2500rpm.
10. preparation method as described in claim 1, which is characterized in that in step (2), the curing is with 1000-
The revolving speed of 1500rpm stirs 6-10 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096443A (en) * | 2007-07-10 | 2008-01-02 | 武汉理工大学 | Method for preparing epoxy sheet mould plastic |
| CN101608053A (en) * | 2008-06-20 | 2009-12-23 | 太阳油墨制造株式会社 | Hot curing resin composition |
| CN101798438A (en) * | 2009-02-06 | 2010-08-11 | 太阳油墨制造株式会社 | Heat curable resin composition, dry film and printed wiring board and method for preparing the same |
| CN102796478A (en) * | 2012-08-03 | 2012-11-28 | 金安国纪科技股份有限公司 | Copper foil clad laminated board with UV shielding function, adhesive and preparation methods thereof |
-
2016
- 2016-08-29 CN CN201610752393.0A patent/CN106398116B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096443A (en) * | 2007-07-10 | 2008-01-02 | 武汉理工大学 | Method for preparing epoxy sheet mould plastic |
| CN101608053A (en) * | 2008-06-20 | 2009-12-23 | 太阳油墨制造株式会社 | Hot curing resin composition |
| CN101798438A (en) * | 2009-02-06 | 2010-08-11 | 太阳油墨制造株式会社 | Heat curable resin composition, dry film and printed wiring board and method for preparing the same |
| CN102796478A (en) * | 2012-08-03 | 2012-11-28 | 金安国纪科技股份有限公司 | Copper foil clad laminated board with UV shielding function, adhesive and preparation methods thereof |
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